Method for the improving of goods



Patented May 14,1940

UNITED STATES PATENT OFFICE METHOD FOR THE IMPROVING OF GOODS ofSwitzerland No Drawing. Application July 6, 1938, Serial No. 217,720. InGermany July 6, 1937 10 Claims.

It has been found that or the protection of goods from attacks of verminthose quaternary ammonium compounds are particularly suitable whichcontain on the nitrogen atom no less than two aryl-methyl groups, atleast one of which is to bear one or several hydroxyl groups which maybeeventually alkoxylated or esterified.

' The compounds suggested for the treatment of goods for improvingpurposes are of the general formula An AT-CH3ITC [is-A110" In thisformula Ar and Ari mean aromatic residues such as phenyl, diphenyl,naphthyl, tetra hydronaphthyl, octahydro-anthracyl and the like. R1 andR2 mean any organic-residues e. g. aliphatic residues such as methyl-,ethyl-, hydroxyethyl-, dimethyl-amino-ethyl-, propyl-,

isopropyl-, benzyl-groups and the like; R1 and R2 pounds in which thearomatic residues are substituted by higher alkylor cyclo-alkyl-groupsare most suitable. 7

Such compounds are e. g. dimethyl-benzyl- (2'- hydroxy-E-chloro-benzyl)-ammonium chloride, 5,5-dihydroxye2,2'-dichloro-dibenzy1-piperidiniumchloride, 5-chloro-2-hydroxybenzyl-a-menaphthyl-diethyl-ammoniumchloride, 4,6324,- tetrachloro 1 hydroxydibenzyl-diethyl-ammoniumchloride,- 5 -bromo- 2 -methyl-4chloro1- hydroxy-dibenzyl-piperidiniumchloride. They are obtained by converting amines containing at least onearylmethyl group into-quaternary ammonium compounds in a way usual initself,v

whereat the materials are to be selected in such a. manner, that thereexists in the quaternary ammonium compound at least 2 arylmethyl groups,at least one of which is substituted by one phenolic hydrozwl group orby its functional derivatives such as esteror other groups. But I maylikewise proceed by starting with the amines which already possess twoarylmethyl groups of the characterized sort and then converting theseinto the quaternary compounds e. g. by converting them with alkylatingor aralkylating agents. Finally it is also practicable to react primaryand secondary amines containing no arylmethyl groups with compoundswhich while forming the quaternary ammonium compounds give oil thearylmethyl groups of the characterizod type.

The compounds suggested for the refining of goods can be applied eitheralone or mixed with one another and eventually with an addition of otherpreserving agents. I may proceed e. g. in such a manner that I soak ormoisten or sprinkle the goods to be preserved with solutions of saidcompounds in organic liquids. With products inclining to crystallizing Iam in a position to prevent the efiiorescing of the ammonium compoundsin choosing an appropriate solvent or mixture of solvents or alsoadditional materials such as higher alcohols, cyclic acetones or acetalsand the like.

Moreover these compounds may be used in emulsions or dispersions orwhere they are easily soluble in water-An aqueous solutions to beapplied in the treatment of the goods in a way similar to a dyeingprocess.

It may sometimes be advisable to co-employ some special wettingandemulsifying-agents to secure a uniform penetration of the goods.

I may bring the goods into intimate contact with the new preservingagents also by powdering them. In the powdering process I may make useof dredging boxes, rolling casks and the like. When it is not advisableto use my novel preservation per se in the form of a powder, I can makefirm powdery preparations out of same and powdered adsorption materialssuch as infusorial earth, talcum, wood-flour, bleaching earth, starch,etc.

My new preserving agents may be applied in the presence of othercompounds such as acids,

' salts, mordants, dyestufis and the like, whereby their efil'ciency ortheir sticking-power will be enhanced or other properties improved.

The treatment can be performed at room temperature as well as at highertemperatures.

Due to the simplicity of the present method the treatment is possiblenot only in the manufacture and working-up of goods but also in thehousehold and incleansing-establishments such as chemical laundries,further in washing with benzine or with other organic solvents andparticularly with non-inflammable ones.

I I may also apply, besides the aforesaid hydrohalic acids, other acidssuch as hydrofluosilicic acid, perchloric acid, hydrocyanic acid, acylephosphoric acid, sulfuric acidor also organic acids e. g. carbonicacids, sulfonic acids, etc, to form salts with my quaternary bases.

The claimed products may serve for the refining of wool, textilematerials, natural or artificial fibres, iurriery, hair, feathers,leather, paper or, respectively, products or masses containing suchmaterials. Their preserving power is so high that small amounts aresufficient to produce very remarkable effects.

Example I Furs to be preserved against vermin and particularly againstmoths are powdered with a mi):- ture consisting of 93 weight parts oftalcum and 7 weight parts of5-bromo-2-rnethylr-chloro-lhydroxy-dibenzyl-piperidinium chloride.

Example 2 W001, becomes unassailable by vermin when treated with threetimes the amount of a 0.2%- aqueous-alcoholic solution of4,6,3',e'-mtrachlorol-hydroxy-dibenzyl-diethyl-ammonium-chloride.

Example 3 Textiles are thoroughly moistened, as indicated in Example 2,with a 0.5%-aqueous solution ofdimethy1-benzyl-(2-hydroxy-5-chlorobenzyD-ammonium-chloride andsubsequently treated in a diluted aqueous solution of potassiumchlorate, whereby the difficultly soluble perchlorate of the quaternarybase is precipitated upon the goods to be preserved against vermin.

I claim:

1. Process for the protection of goods from vermin characterized bytreating the goods with quaternary ammonium compounds of the generalformula An ..r-cn,-1 -cHT-Anon in which Ar and Ari mean an aromaticresidue, An means an anion and R1 and R: stand for any organic residue.

2. Process for the protection of goods from vermin characterized bytreating the goods with quaternary ammonium compounds of the generalformula Air: A l. C Hr-f-C H;Ar;-O H

R; R: in which Ar and Ari mean an aromatic residue, An means an anionand R1 and R2 stand for organic residue, which jointly form a ring withthe N-atom.

3. Process for the protection of goods from vermin characterized bytreating the goods with soluble quaternary ammonium compounds of thegeneral formula in which Ar and Ari. meanan aromatic residue,

An means an anion and R1 and R2 stand for any organic residue andreacifing the soluble quaternary ammonium compounds on the goods withsalts producing dimcultly soluble salts with the quaternary ammoniumcompounds by double decomposition.

4. A vermin-proofing agent for goods comprising a quaternary ammoniumcompound or" the general formula in which Ar and Ari mean anysubstituted aromatic residue, An means an anion oi the group consistingof Cl, Fl, Br and I and R1 and R2 stand for organic residue jointlyforming a ring with the N-atom.

6. A vermin-proofing agent for goods comprising a quaternary ammoniumcompound of the general formula.

in Hg in which Ar and Ari mean a substituted aromatic residue of thegroup consisting of hydroxyl-, halogen-, nitro-, amino-, alkylandcycloallzyl substituted aromatic residues, An means an anion and B1 andR2 stand for any substituted aliphatic residue, the hydrogen atoms ofthe CH; groups being substituted by allryl residues.

'7. A vermin-proofing agent for goods containing5-bromo-2-methy1--chloro-i-hydroXy-dibenzyl-piperidiniumchloride.

8. A vermin-proofing agent for goods containing 4, G, 3,F-tetrachloro-lhydroxy-ciibenzyl-diethyl-ammonium chloride.

9. A vermin-proofing agent for goods containingdimethyl-benzyl-(Z-hydroxy-fi-chiorcbenzyll ammoniumchloride.

l0. Vermin-prooied goods of the nature of furs, feathers, textiles andother fibrous materials and the like, having their vermin-proofcharacteristics imparted by incorporating in said goods a compound ofthe formula.

in which Ar and Ari mean aromatic groups, An means a halogen and R1 andR2 stand for an organic radical.

WINFRID HENTRICH.

